Process for aldehydo isomerization of olefin alpha oxides



Patented Sept. 5, 1950 PROCESS FOR ALDEHYDO ISOMERIZATION F OLEFIN ALPHA OXIDES Edward C. Jacobs, San Mateo, Calif., and Lester G. Lundsted, Grosse Ile, Mich., assignors to Wyandotte Chemicals Corporation, Wyandotte, Mich, a corporation of Michigan No Drawing.

Original application March 11,

1947, Serial No. 733,976. Divided and this application July 23, 1949, Serial No. 106,506

4 Claims. (Cl. 260*601) This application is a division of our co-pending application Serial No. 733,976, filed March 11, 1947.

The present invention relates to the isomerization of alkylene alpha oxides (1,2 alkylene oxides), in which the principal and predominant product is the saturated aldehyde isomer of the oxide. The invention also relates to a catalyst composition particularly suited for such aldehydo-isomerization.

In the co-pending U. S. patent application Serial No. 588,710, filed April 16, 1945, now matured to Patent No. 2,479,632, August 23, 1949, by Lester G. Lundsted, Edward J. Schwoegler and Edward C. Jacobs, said Lundsted and Jacobs being co-applicants herein, it is disclosed that a chromic oxide gel catalyst (prepared as described in vol. 6 3, p. 1129, of the Journal of the American Chemical Society) efiects the isomerization of propylene oxide to allyl alcohol, propionaldehyde being the minor and less-proportion product. In other words, in the aforesaid co-pending application, the employment of the chromic oxide gel catalyst alone produced an alkylene oxide isomerization in which the ratio of allyl alcohol to the propionaldehyde was on the order of 3 to 1. We have now discovered, that by the incorporation of certain specified compounds and oxides of cadmium, tungsten and iron, this relationship can be reversed; and even to the point where, in the case of propylene oxide, there is practically no allyl alcohol and the propionaldehyde constitutes over 90% of the conversion products. The isomerization process and catalyst composition of our invention also results in exceptionally high and favorable conversion percentages.

The catalyst compositions of our invention are also particularly useful and advantageous in that they possess relatively long lives of activity; and upon regeneration treatment, have the ability of resuming or recapturing an activity paramountto that of the originally prepared catalyst composition.

Briefly outlined, our invention comprises passing an alkylene alpha oxide, preferably ethylene oxide or propylene alpha oxide, in the vapor phase, and at a space velocity in the range of 90-1600 grams per hour per liter of catalyst and at a temperature of 180-400'C., over a catalyst composition consisting of a dried or dehydrated chromic oxide gel to which there has been added two of the following compounds: cadmium chloride, cadmium oxide, tungsten oxide and iron oxide. Preferably cadmium chloride and cadare present as a derivative of a soluble Cr-, W-,

or Fe-, salt or oxy-acid subsequently converted to the precipitated metallic oxide by treatment with ammonium hydroxide.

Preferably, the proportions of the above-named metallic compound ingredients of our gel catalyst composition, are found to fall in certain specified ranges. The determination of the proportion of these compounds is conveniently based upon a calculation of the chemically equivalent weights,

of the corresponding metallic compounds employed in the synthesis of the catalyst compositions, and thence reduced to simplified or empirical chemical formulas, such as CrzOs, CdClz, CdO, W03 and F6203; and even though the actual chemical structure of the metallic compound components of the catalyst compositions is presently unknown, escaping precise chemical analysis. Thus, the preferred range of propertions of these ingredients is as follows: @203, 40-70% by weight; CdClz, 30-45%; .CdO, 10-30%; W03, 15-50%; and F6203, 13%.

In carrying out the process of our invention, the catalyst need not be admixed with, supported upon, or carried by a so-called catalyst carrier, but is placed directly in a furnace or heating chamber (preferably mounted in a vertical position) with externally applied heat, andthe vaporized or gaseous alkylene oxide then passed over and through the heated catalyst. A

The following examples further illustrate our invention:

Example 1 to the solution 413 cc. of concentrated ammonium hydroxide solution (28% by weight NI-Is content) diluted with 1.2 liters of distilled water. This i? water to reniove N03 ions. One hundred grams of tungstic acid, dissolved in concentrated ammonium hydroxide were then added to the washed gel and the resultant composition baked to dry ness in an oven at 240 C.

The composition of the resultant catalyst was calculated to be:

CrzOs, 51 mols or 49.6% by weight W03, 33.3 mols or 49.4% by weight F8203, 1 mol or 1.0% by weight Propylene alpha oxide was passed over this catalyst at a temperature of 350 C. and at a space velocity of 95 grams per hour per liter of catalyst. The conversion, on the basis of the total amount of propylene alpha oxide fed through the heated catalyst chamber was 36% to propionaldehyde (based on carbonyl analysis), 6% to unsaturates, as allyl alcohol.

Example 5 In the catalyst composition employed in this example, the relative proportions of tungsten oxide and iron oxide added to the parent chromic oxide gel, were reduced. The preparation of the catalyst composition was similar to that previously described in Example 4. The resultant composition, on a calculated basis, contained:

CrzOa, 51 mols or 69.7% by weight W03, 13.7 mols or 28.7% by weight F8203, 1 mol or 1.6% by weight On passing propylene alpha oxide over the above catalyst at a temperature of 350 C. and at a space velocity of 110 grams per hour per liter of catalyst, the furnace products were found to contain 63% propionaldehyde and 17% unsaturates.

Example 6 In the catalyst composition employed in this example the same catalyst of Example 4 was used except that after baking to dryness in an oven at 240 C., the dried gel was subsequently heated to a temperature of 1000-1200 C. Ninety cc. of the resultant heated catalyst (i. e. 51 mols CrzOz, 33.3 mols W03 and 1 mol F6203) were placed in the tubular furnace. Propylene alpha oxide passed over this catalyst composition at a temperature of 214-292 C. (temperature readings taken at increments of 1 inch apart through a 6 inch depth of catalyst bed), and at a space velocity of 708 grams per hour per liter of catalyst. After so passing the vaporized propylene alpha oxide over the heated catalyst for a period of 4 hours and 20 minutes, the following results were obtained: 66.3% conversion of propylene alpha oxide fed of which conversion products 86.8% was propionaldehyde and 7.35% was unsaturate's; or on the basis of per cent of furnace products 57.5% propionaldehyde and 4.8% unsaturates.

Example 7 Fe(NOa)a.9Ha0 were dissolved in 1% liters ofwater, heated to the boiling point and cooled; whereupon 413 cc. of concentrated ammonium hydroxide (28% NH: content) were added, forming a gel. The resultant gel was baked in an oven at 58 C. for 48 hours, then washedfree oi nitrate ions, drained and a solution of 40 grams of tungs'tic acid in cc. of concentrated ammonium hydroxide solution was stirred in. The resultant mixture was then baked at 250 C. for approximately 96 hours, producing a hard, black product, which was thereafter heated to 450 C. for 3 hours.

The resultant catalyst composition contained the following (calculated basis) (111203-132 mols or 67.8% by weight Woe-3.8 mols or 29.4% by weight Fe20a-1 mol or 2.8% by weight On passing propylene alpha oxide over the above described catalyst composition at a temperature of 350 C. and at a space velocity of 296 grams per hour per liter of catalyst, the furnace products contained 55.6% propionaldehyde and 8.7% unsaturates.

For the purpose of summarizing the foregoing Examples 1-7 inc. the following table is given showing the respective amounts of catalyst composition ingredients, and the per cent of the propionaldehyde (based on carbonyl analysis) and of unsaturates, as allyl alcohol, of the furnace products.

From this table, it will be seen that the propionaldehyde constitutes the major and predominant product in each case, with the unsaturates (analyzed as allyl alcohol) being in a minor proportion. In the majority of cases the ratio of the propionaldehyde to unsaturates (of. Examples 1-5 and 7), is 6 to 1 or greater. It will also be seen that the percentage proportions of catalyst constituents confirm the preferred range of proportions stated at the outset of this description.

Table Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Constituents M Q1 Perefint M 0} Percyent M Q1 Pe rgint M 01 Pogo-g ant M 01 Pefgint M 0.1 Peg ent M 01 Pei-)cyent Ratio weight Ratio weight Ratio weight Ratio weight Ratio weight Ratio weight Ratio weight 43. 5 4. 2 56. 5 5. 6 56. 7 51 49. 6 51. 0 69. 7 51 49. 6 l3. 2 (i7. 8 41. 9 2.0 32. 2 14.6 1.0 11.3 3.2 27.7 1. 0 15. 6 33. 3 49. 4 l3. 7 28. 7 33. 3 49. 4 3. 8 29. 4 1.0 1.0 1.0 1.6 1.0 1.6 1.0 2.8

PER CENT OF FURNACE PRODUCTS Propionaldehyde 67. 0 80. 3 63. 0 36. 0 63. 0 57. 5 55. 6 Unsatnrates. 0. 43 3. 2 l0. 7 6. 0 l7. 0 4. 8 8. 7

mum;

irm yedl re the, olefin! a nha' Q 1% W passed over the chromic 'oxide-cadiniu1 r 1 cliloj' ride-cadmium oxide catalyst composition of EX- ample 1. I

The; e hylene 44 alter; ehea in o h we nha er. 34$: m ssed: W he" at 'stsri ed aha ame eloci y o 9.01 eramsin e 91; net liter of catalyst. The temperaturepi, the heapw me umace aemaintainedi y ensrqf an: autamatiq controh at 2 50? Q. During. the course t hei-m rita hseryedi ha eaame mature of; .2? C, w s; at ain db n-i hee c alyst. bed; mas ec li edsn tr n re Q -I he: eth lene xidflllflifl di o h iaytaly t n il qsl ion, 85 was p x ntednand of: hei a rnapeinm ucpe, 5%; o sisted; of. aceta da iyda Omen mode-stf agnlying; he, nr n irglef 01 inve tion het m cy dl hangeeb ine ma e. 3& mean sg th details desc b d nrQ dwhe mama sta ed Qi-v he t lq fle a ms or mumalent 0f; ueh: be emnl ye y;

= W b eremmi: pan iculary y mint: ut nd 1 tinctly claim as our invention:

.. The; process; Qilqroduc n a deh des from o efi a pha ee hi heco mes heatine; a d

oxides. in contact with a catalyst compositioh derived from a;- clehydrateda ammoniacal gel mix- 8ft tune; o fchnmnle: oxide, cadmiurm chloride and cadmiumxoxidca 2 Themrocesseotrproducing; the. corresponding; saturatedialtlehydesirom; propylene alpha. oxide. and ethylene oxide which compriseapassing the oxide. 61133.81. spacei. velocity of: 90.11.600 grams; I1 hour per liter of catalyst, at a tenmera/fiure:0f-. 409), C, 0vep a caigalyspcpmpoeitign derived from eh ra ed. mmon a a fe mi of chromio oxidg cad migm chloride and, cadmium oxide.

3% The-pmcessgofmroducing acetaldehydegirom ethylene oxide which comprises passingzsaid: oxide at a temperature: of 250P-300,".G.-, overflae catalyst composition derived from adehydrated; ammoniacal gel; mixtureeofi 'chromic. oxide; cadmium chloride and cadmiumwxidei 4- The processor producing pmpionaldehyde; from propylenee alpha, oxide; whichcomprises, passing the oxide atga spaee velocity of 350-540 grams per hour per liter of catalyst, at a temperatu eotapproximately= 300$ overia catalyst cbmposit-ion derived" from a; dehydrated? any-- moniacal gel mixture 0g chromic oxide,- cadmium chloride and cadmium oxide;

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1. THE PROCESS OF PRODUCING ALDEHYDES FROM OLEFIN ALPHA OXIDES WHICH COMPRISES HEATING SAID OXIDES IN CONTACT WITH A CATALYST COMPOSITION DERIVED FROM A DEHYDRATED, AMMONIACAL GEL MIXTURE OF CHROMIC OXIDE, CADMIUM CHLORIDE AND CADMIUM OXIDE. 